Molecular and oligomeric silane precursors to network materials

ABSTRACT

The present invention pertains to molecular and oligomeric organo-silicon compounds bearing fluorine atoms, soluble in fluorinated solvents and useful as precursors to network materials.

This application claims the priority benefit of U.S. Provisional Application 60/000,574, filed Jun. 28, 1995.

BACKGROUND OF THE INVENTION

This invention concerns organosilicon compounds and in particular concerns novel molecular and oligomeric organosilicon compounds bearing fluorine atoms.

Various kinds of fluorine-bearing organosilicon compounds are known in organosilicon chemistry including, for example, simple fluorine-containing alkoxysilanes such as fluoroalkoxysilanes of the formula (R_(f) CH₂ O)₄ Si, wherein R_(f) =CF₃ to C₁₀ F₂₁, disclosed in U.S. Pat. No. 2,993,925; (CF₃ (CF₂)_(x) CX₂ CH₂ CH₂ O)₄ Si(x=0-4 and X=H or F) in U.S. Pat. No. 3,491,134; and HSi(OCH₂ CF₃)₃ and CH₂ ═CHSi(OCH₂ CF₃)₃ in U.S. Pat. No. 4,652,663.

U.S. Pat. No. 5,378,790 describes more complex compounds, called "stars", of the formula X(SiQ₃)_(n) wherein Q is C₁ to about C₈ alkoxy, C₁ to about C₈ acyloxy, or halogen. However, a fluoroalkoxy Q is not described in this patent and processes for the preparation of precursors with a fluoroalkoxy Q are not provided.

There has also been great interest in recent years in polymers with a regular, three-dimensional, treelike structure. Such polymers are called dendrimers. These tree-like molecules are the result of a controlled repetitive growth starting from a polyfunctional core. From the core, two or more identical branches emanate, each branch containing further branch sites at its end. With successive generations a fractal, ball-like structure evolves until further growth is limited by surface congestion. While most of such polymers are wholly organic, a few organosilicon dendrimers have been prepared. D. Seyferth et al., in "Synthesis of an Organosilicon Dendrimer Containing 324 Si--H Bonds", Organometallics 1994, 13, 2682-2690 describe starting with tetravinylsilane as a core molecule, a succession of alternate Pt-catalyzed hydrosilylations of all vinyl groups with HSiCl₃ and vinylations of all of the SiCl groups introduced with CH₂ ═CHMgBr in tetrahydrofuran providing a divergent synthesis of four generations of polycarbosilane dendrimers in which the Si atoms are linked by CH₂ CH₂ groups. The chlorosilane of each generation was reduced with LiAlH₄ to the corresponding silicon hydride. Compounds with fluorinated ends or fluoroalkoxy or alkoxy ends are not mentioned or enabled.

Applicant has prepared novel fluorine-bearing organosilicon compounds of he "star" and "dendrimer" type and novel fluorine-bearing polysilicates which are particularly useful in nonconventional sol-gel chemistry conducted in fluorinated solvents.

SUMMARY OF THE INVENTION

The present invention provides a compound of formula I

    X(Si(OC.sub.a H.sub.2a R.sub.f).sub.3).sub.n               I

wherein:

X is at least one organic link selected from the group consisting of:

(a) R¹ _(m) SiY_(4-m) ;

(b) ring structures ##STR1## (c) R¹ _(m) Si(OSi(CH₃)₂ Y)_(4-m) ; (d) CH₃ SiY₂ OSiY₂ CH₃ ;

(e) Y₃ SiOSiY₃ ;

(f) Y₂ (CH₃)Si(CH₂)_(b) Si(CH₃)Y₂ ;

(g) Y₃ Si(CH₂)_(b) SiY₃ ;

(h) Y₃ SiC₆ H₄ SiY₃ ;

(i) substituted benzene, including all isomers, selected from the group consisting of:

(i) C₆ H₃ (SiZ_(3-c) Y_(c))₃ ;

(ii) C₆ H₂ (SiZ_(3-c) Y_(c))₄ ;

(iii) C₆ H(SiZ_(3-c) Y_(c))₅ ; and

(iv) C₆ (SiZ_(3-c) Y_(c))₆ ; and

(j) substituted cyclohexane, including all stereoisomers, selected from the group consisting of:

(i) 1,2-C₆ H₁₀ (Y)₂ ; 1,3-C₆ H₁₀ (Y)₂ ; 1,4-C₆ H₁₀ (Y)₂ ;

(ii) 1,2,4-C₆ H₉ (Y)₃ ; 1,2,3-C₆ H₉ (Y)₃ ; 1,3,5-C₆ H₉ (Y)₃ ;

(iii) 1,2,3,4-C₆ H₈ (Y)₄ ; 1,2,4, 5-C₆ H₈ (Y)₄ ; 1,2,3,5-C₆ H₉ (Y)₄ ;

(iv) 1,2,3,4,5-C₆ H₇ (Y)₅ ; and

(v) C₆ H₆ (Y)₆ ; and

(k) Y(CF₂)_(v) Y

R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_(q) --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

wherein up to 50% of the fluorine of the R_(f) group is optionally substituted with hydrogen;

a is an integer from 1 to about 10;

b is an integer from 1 to about 10;

c is 1, 2 or 3;

m is 0, 1 or 2;

n is an integer greater than or equal to 2;

v is an even integer from 2 to about 14;

R¹ is C₁ to about C₈ alkyl or aryl;

Y is --(CR² R³)_(k) CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_(h) --

R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl, or aryl, provided that at least one of R⁴ to R⁷ is hydrogen;

k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; and

Z is C₁ to about C₄ alkyl, 3,3,3-trifluoropropyl, aralkyl or aryl.

The present invention also provides a compound of formula IA

    X(R.sup.10 Si(OC.sub.a H.sub.2a R.sub.f).sub.2).sub.n      IA

wherein:

X is at least one organic link selected from the group consisting of:

(a) R¹ _(m) SiY_(4-m) ;

(b) ring structures ##STR2## (c) R¹ _(m) Si(OSi(CH₃)₂ Y )_(4-m) ; (d) CH₃ SiY₂ OSiY₂ CH₃ ;

(e) Y₃ SiOSiY₃ ;

(f) Y₂ (CH₃)Si(CH₂)_(b) Si(CH₃)Y₂ ;

(g) Y₃ Si(CH₂)_(b) SiY₃ ;

(h) Y₃ SiC₆ H₄ SiY₃ ;

(i) substituted benzene, including all isomers, selected from the group consisting of:

(i) C₆ H₃ (SiZ_(3-c) Y_(c))₃ ;

(ii) C₆ H₂ (SiZ_(3-c) Y_(c))₄ ;

(iii) C₆ H(SiZ_(3-c) Y_(c))₅ ; and

(iv) C₆ (SiZ_(3-c) Y_(c))₆ ; and

(j) substituted cyclohexane, including all stereoisomers, selected from the group consisting of:

(i) 1,2-C₆ H₁₀ (Y)₂ ; 1,3-C₆ H₁₀ (Y)₂ ; 1,4-C₆ H₁₀ (Y)₂ ;

(ii) 1,2,4-C₆ H₉ (Y)₃ ; 1,2,3-C₆ H₉ (Y)₃ ; 1,3,5-C₆ H₉ (Y)₃ ;

(iii) 1,2,3,4-C₆ H₈ (Y)₄ ; 1,2,4,5-C₆ H₈ (Y)₄ ; 1,2,3,5-C₆ H₉ (Y)₄ ;

(iv) 1,2,3,4,5-C₆ H₇ (Y)₅ ; and

(v) C₆ H₆ (Y)₆ ;

R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ (CF₂ O)_(q) --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

wherein up to 50% of the fluorine of the R_(f) group is optionally substituted with hydrogen;

Z is C₁ to about C₄ alkyl, 3,3,3-trifluoropropyl, aralkyl or aryl;

Y is --(CR² R³)_(k) CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_(h) --;

R¹ is C₁ to about C₈ alkyl or aryl;

R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl or aryl, provided that at least one of R⁴ to R⁷ is hydrogen;

R¹⁰ is C₁ to about C₈ alkyl or C_(a) H_(2a) R_(f) ;

m is 0, 1 or 2;

k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero;

a is an integer from 1 to about 10;

b is an integer from 1 to about 10;

c is 1, 2 or 3; and

n is an integer greater than or equal to 2.

The present invention also provides a compound of formula II

    Si (CH.sub.2).sub.f Si(CH.sub.3).sub.3-d ((CH.sub.2).sub.e Si(OR.sup.10).sub.d !.sub.4                               II

wherein:

dis 1, 2 or 3;

e is an integer from 2 to about 10;

f is an integer from 2 to about 10;

R¹⁰ is C₁ to about C₈ alkyl or C_(a) H_(2a) R_(f) ;

a is an integer from 1 to about 10;

R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_(q) --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

wherein up to 50% of the fluorine of the R_(f) group is optionally substituted with hydrogen.

The present invention further provides an oligomeric compound of formula III

    Si(OC.sub.a H.sub.2a R.sub.f).sub.4-z O.sub.z/2            III

wherein:

z is a number from 0.5 to 3.0;

a is an integer from 1 to about 10; and

R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ O)_(q) --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

wherein up to 50% of the fluorine of the R_(f) group is optionally substituted with hydrogen.

The present invention also provides an oligomeric compound of formula IV

    R.sub.f -(CH.sub.2).sub.y --Si(OR.sup.14).sub.3-z O.sub.z/2IV

wherein:

z is a number from 0.5 to 2.5;

y is an integer from 2 to about 10;

each R¹⁴ is independently C₁ to about C₈ alkyl, C₁ to about C₁₀ carboxy, C₁ to about C₁₀ fluorocarboxy or C_(a) H_(2a) R_(f) ;

a is an integer from. 1 to about 10; and

R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ (CF₂ --O)_(q) --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ; wherein up to 50% of the fluorine of the R_(f) group is optionally substituted with hydrogen.

DETAILED DESCRIPTION

For the compounds of formula I, IA, II, III and IV as defined above, the R_(f) group can be a fluoroalkyl or perfluoroalkyl group, which can be either normal or branched, and has up to about 18 carbon atoms, preferably one to eight carbon atoms, especially preferred one to three carbon atoms. Normal perfluoroalkyl groups include, for example, trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorodecyl, perfluorododecyl, and perfluorooctadecyl. R_(f) is preferably CF₃, C₂ F₅ or C₃ F₇. Fluorine-bearing compounds of formulas I, IA, II, III and IV where R_(f) has more than eighteen carbon atoms are considered less practical to synthesize, although such fluorosilanes would be perfectly suitable in all applications contemplated for this class of compounds. A typical suitable branched fluoroalkyl group is --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃.

The R_(f) groups also can be certain perfluoro(alkyleneoxy)alkyl)radicals. These include perfluoro(methylene(polymethyleneoxy)methyl) radicals (c) and perfluoro((polyisopropyleneoxy)propyl) radicals (b).

For the compounds of formula I and IA, X is preferably (a) R¹ _(m) SiY_(4-m) ; the ring structures of formula Ib(i)-(iii) and IA(b)(i)-(iii); (c) R¹ _(m) Si(OSi(CH₃)₂ Y)_(4-m) or (k) Y(CF₂)_(v) Y. The most preferred organic link X, is where m is 0, k is 0 or 1, h is 0 or 1, and all of R² to R⁹ are hydrogen. R_(f) is preferably CF₃, C₂ F₅ or n-C₃ F₇. Z is preferably CH₃ ; the preferred aralkyl being benzyl and the preferred aryl being phenyl. n is preferably 2-6, most preferably 2, 3 or 4; a is preferably 1; and v is preferably 4, 6, 8 or 10, most preferably 6.

Representative examples of compounds of formula I are:

Si(CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ ;

Si(CH₂ CH₂ Si(OCH₂ CF₂ CF₃)₃)₄ ;

Si(CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ ;

cyclo-((CH₃)(CF₃ CH₂ O)₃ SiCH₂ CH₂)SiO)₄ ;

cyclo-((CH₃)(CF₃ CH₂ O)₃ SiCH₂ CH₂ CH₂)SiO)₄ ;

cyclo-((CH₃)(CF₃ CH₂ O)₃ SiCH₂ CH₂ CH₂)SiO)₅ ;

cyclo-(CH₃ (CF₃ (CF₂)₂ CH₂ O)₃ SiCH₂ CH₂)SiO)₄ ;

(CF₃ CH₂ O)₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si(OCH₂ CF₃)₃ ;

(CF₃ (CF₂)₂ CH₂ O)₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃ ; and

(CF₃ CH₂ O)₃ Si(CH₂)₆ (CF₂)₆ (CH₂)₆ Si(OCH₂ CF₃)₃.

Representative examples of formula IA are:

Si(CH₂ CH₂ SiCH₃ (OCH₂ CF₃)₂)₄ ;

Si(CH₂ CH₂ SiCH₃ (OCH₂ (CF₂)₂ CF₃)₂)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ SiCH₃ (OCH₂ CF₃)₂)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ SiCH₃ (OCH₂ (CF₂)₂ CF₃)₂)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ CH₂ SiCH₃ (OCH₂ CF₃)₂)₄ ;

(CF₃ CH₂ O)₂ CH₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ SiCH₃ (OCH₂ CF₃)₂ ;

(CF₃ (CF₂)₂ CH₂ O)₂ CH₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ SiCH₃ (OCH₂ (CF₂)₂ CF₃)₂ ;

(CF₃ CH₂ O)₂ CH₃ Si(CH₂)₆ (CF₂)₆ (CH₂)₆ SiCH₃ (OCH₂ CF₃)₂ ;

Si(CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ CF₃)₂)₄ ;

Si(CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ (CF₂)₂ CF₃)₂)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ CF₃)₂)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ (CF₂)₂ CF₃)₂)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ CF₃)₂)₄ ;

(CF₃ CH₂ O)₂ (CF₃ CF₂ CH₂ CH₂)SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ CF₃)₂ ;

(CF₃ (CF₂)₂ CH₂ O)₂ (CF₃ CF₂ CH₂ CH₂)SiCH₂ CH₂ (CF₂)₆ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ (CF₂)₂ CF₃)₃ ;

(CF₃ CH₂ O)₂ (CF₃ CF₂ CH₂)Si(CH₂)Si(CH₂)₆ (CF₂)₆ (CH₂)₆ Si(CH₂ CF₂ CF₃)(OCH₂ CF₃)₂ ;

cyclo-((CH₃)(CF₃ CH₂ O)₂ CH₃ SiCH₂ CH₂)SiO)₄ ;

cyclo-((CH₃)(CF₃ CH₂ O)₂ CH₃ SiCH₂ CH₂ CH₂)SiO)₄ ;

cyclo-((CH₃)(CF₃ CH₂ O)₂ CH₃ SiCH₂ CH₂ CH₂)SiO)₅ ; and

cyclo-((CH₃)(CF₃ (CF₂)₂ CH₂ O)₂ SiCH₂ CH₂)SiO)₄.

For the compounds of formula II as defined above, preferably f is 2 or 3; e is preferably 2 or 3; and R¹⁰ is preferably CH₂ CF₃, CH₂ C₂ F₅, or CH₂ C₃ F₇.

Representative examples of formula II are

Si(CH₂ CH₂ CH₂ Si(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃)₄ ;

Si(CH₂ CH₂ CH₂ Si(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ ;

Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃)₂)₄ ;

Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₂)₄ ; and

Si(CH₂ CH₂ CH₂ Si(CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₃)₄.

Preferably the fluoroalkoxysilanes of formula I, formula IA and formula II are soluble in one or more fluorinated solvents. Perfluoro aliphatic (e.g., perfluoro(butyl THF)), polyfluoro aliphatic (e.g., C₃ F₇ O CHFCF₃) and perfluoroaromatic (e.g., hexafluorobenzene) solvent systems can be utilized. Preferred solvents comprise perfluoro(butyl THF), e.g., "FLUORINERT" FC-75; "FLUORINERT" FC-40, a mixture of perfluoroalkylamines; perfluoro phenanthrene, e.g. "FLUTEC" PP-11; C₃ F₇ O CHFCF₃, e.g., "FREON" E1; hexafluorobenzene (C₆ F₆); perfluoromethylcyclohexane, C₆ F₁₁ (CF₃); and perfluoro(n-ethylmorpholine). The solubility of compounds of formula I were determined in hexafluorobenzene (C₆ F₆), perfluoro(butyl THF) (FC-75), hexane, and tetrahydrofuran (THF) and are shown below in Table I.

                  TABLE I                                                          ______________________________________                                         Solubility of Fluoroalkoxy Silanes                                             Compound           C.sub.6 F.sub.6                                                                       FC-75   Hexane                                                                               THF                                    ______________________________________                                         Si(CH.sub.2 CH.sub.2 Si(OCH.sub.2 CF.sub.3).sub.3).sub.4                                          Y      N       N     Y                                      Si(CH.sub.2 CH.sub.2 Si(OCH.sub.2 C.sub.3 F.sub.7).sub.3).sub.4                                   Y      Y       N     N                                      (CH.sub.3 (CH.sub.2 CH.sub.2 Si(OCH.sub.2 CF.sub.3).sub.3)SiO).sub.4                              Y      N       N     Y                                      (CH.sub.3 (CH.sub.2 CH.sub.2 Si(OCH.sub.2 C.sub.3 F.sub.7).sub.3)SiO).sub.     4                  Y      Y       N     Y                                      Si(OSi(CH.sub.3).sub.2 CH.sub.2 CH.sub.2 Si(OCH.sub.2 CF.sub.3).sub.3).sub     .4                 Y      N       N     Y                                      Si(OSi(CH.sub.3).sub.2 CH.sub.2 CH.sub.2 Si(OCH.sub.2 C.sub.3 F.sub.7).sub     .3).sub.4          Y      Y       N     Y                                       (CF.sub.2).sub.3 CH.sub.2 CH.sub.2 Si(OCH.sub.2 CF.sub.3).sub.3 !.sub.2                          Y      N       N     Y                                       (CF.sub.2).sub.3 CH.sub.2 CH.sub.2 Si(OCH.sub.2 C.sub.3 F.sub.7).sub.3        !.sub.2            Y      Y       N     Y                                      ______________________________________                                    

Synthesis of the compounds of formula I and IA are afforded from hydrosilylation reactions, i.e., an addition reaction between a compound containing a Si--H group with a compound containing aliphatic unsaturation, such as an alkene, in the presence of a catalyst or free radical initiator. Precursor segments containing --CH═CH₂ groups react with other precursor segments which contain terminal Si--H bonds.

Either precursor segment can contain the vinyl or other unsaturated group capable of Si--H addition. For example, Si(CH═CH₂)₄ reacts with HSi(OCH₂ CF₃)₃ to form the precursor Si CH₂ CH₂ Si(OCH₂ CF₃)₃ !₄ ; Si(CH═CH₂)₄ reacts with HSiCH₃ (OCH₂ CF₃)₂ to form the precursor Si(CH₂ CH₂ SiCH₃ (OCH₂ CF₃)₂)₄ ; and cyclo- (CH₃)HSiO!₄ reacts with CH₂ ═CH--Si(OCH₂ C₃ F₇)₃ to form the precursor cyclo-((CH₃)(CF₃ (CF₂)₂ CH₂ O)₃ SiCH₂ CH₂)SiO)₄.

All of the following equations provide for preparation of compounds of formula I by addition of a silane across a carbon-carbon double bond for various definitions of X: (Note that preparation of compounds of formula IA proceed in like fashion except that the group Si(R¹⁰)(OC_(a) H_(2a) R_(f))₂ replaces all instances of Si(OC_(a) H_(2a) R_(f))₃.)

(a) when X is R¹ _(m) SiY_(4-m) :

Eqn. 1A:

R¹ mSi (CR² R³)_(k) CR⁴ ═CR⁶ R⁷ !_(4-m) +4-m H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →R¹ _(m) Si (CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ !_(4-m)

Eqn. 1B:

R¹ _(m) Si (CR² R³)_(k) H!4-m+4-m CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →R¹ _(m) Si (CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ !_(4-m)

(b) when X is a ring structure of the type Ib(i), Ib(ii) or Ib(iii), as previously defined, which can be abbreviated (SiO)_(u) Z_(u) (YSi(OC_(a) H_(2a) R_(f))₃)_(u), wherein u=3 for Ib(i), u=4 for Ib(ii), and u=5 for Ib(iii); then

Eqn. 2A:

(SiO)_(u) Z_(u) (CR² R³)_(k) CR⁴ ═CR⁶ R⁷ !_(u) +u H(CR⁹ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →(SiO)_(u) Z_(z) (CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ !_(u)

Eqn. 2B:

(Sio)_(u) Z_(z) (CR² R³)_(k) H!_(u) +u CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →(SiO)_(u) Z_(u) (CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ !_(u)

(c) when X is R¹ _(m) Si(OSi(CH₃)₂ Y)_(4-m)

Eqn. 3A:

R¹ _(m) Si OSi(CH₃)₂ (CR² R³)_(k) CR⁴ ═CR⁶ R⁷ !_(4-m) +4-m H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →R¹ _(m) Si OSi(CH₃)₂ (CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ !_(4-m)

Eqn. 3B:

R¹ _(m) Si OSi(CH₃)₂ (CR² R³)_(k) H!_(4-m) +4-m CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →R¹ _(m) Si OSi(CH₃)₂ (CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ !_(4-m)

(d) when X is CH₃ SiY₂ OSiY₂ CH₃ :

Eqn. 4A:

CH₃ Si((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₂ OSi((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₂ CH₃ +4H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →CH₃ Si((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₂ OSi((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₂ CH₃

Eqn. 4B:

CH₃ Si((CR² R³)_(k) H)₂ OSi((CR² R³)_(k) H)₂ CH₃ +4CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →CH₃ Si((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₂ OSi((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₂ CH₃

(e) when X is Y₃ SiOSiY₃

Eqn 5A:

Si((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₃ OSi((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₃ +6H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →Si((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃ OSi((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃

Eqn. 5B:

Si((CR² R³)_(k) H)₃ OSi((CR² R³)_(k) H)₃ +6CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →Si((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃ OSi((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃

(f) when X is Y₂ (CH₃)Si(CH₂)_(b) Si(CH₃)Y₂

Eqn. 6A:

Si((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₂ (CH₃)(CH₂)_(b) Si((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₂ (CH₃)+4H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →Si((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₂ (CH₃)(CH₂)_(b) Si((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₂ (CH₃)

Eqn. 6B:

Si((CR² R³)_(k) H)₂ (CH₃)(CH₂)_(b) Si((CR² R³)_(k) H)₂ (CH₃)+4CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →Si((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R.sup.()_(h) Si(OC_(a) H_(2a) R_(f))₃)₂ (CH₃)(CH₂)_(b) Si((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃ (CH₃)

(g) when X is Y₃ Si(CH₂)_(b) SiY₃ :

Eqn. 7A:

Si((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₃ (CH₂)_(b) Si((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₃ +6H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →Si((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃ (CH₂)_(b) Si((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃

Eqn. 7B:

Si((CR² R³)_(k) H)₃ (CH₂)_(b) Si((CR² R³)_(k) H)₃ +6CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →Si((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃ (CH₂)_(b) Si((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃

(h) when X is Y₃ SiC₆ H₄ SiY₃ :

Eqn. 8A:

Si((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₃ C₆ H₄ Si((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)₃ +6H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →Si((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃ C₆ H₄ Si((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ ₃

Eqn. 8B:

Si((CR² R³)_(k) H)₃ C₆ H₄ Si((CR² R³)_(k) H)₃ +6CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →Si((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃ C₆ H₄ CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)₃

(i) when X is a substituted benzene structure of the type, as previously defined, which can be abbreviated C₆ H_(6-w) (SiZ_(3-c) Y_(c))_(w), wherein w represents the number of substitutions on the benzene ring:

Eqn. 9A:

w x (OC_(a) H_(2a) R_(f))₃ Si(CR⁸ R⁹)_(h) H+C₆ H_(6-w) SiZ_(3-c) ((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)_(c) !_(w) →C₆ H_(6-w) SiZ_(3-c) ((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)_(c) !_(w)

Eqn. 9B:

w x CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ +C₆ H₆ w SiZ_(3-c) ((CR² R³)_(k) H)_(c) !_(w) →C₆ H_(6-w) SiZ_(3-c) ((CR² R³)_(k) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)_(c) !_(w)

(j) when X is a substituted cyclohexane of the type, as previously defined, which can be abbreviated C₆ H_(12-w) Y_(w), wherein w is the number of substituents; then:

Eqn. 10A:

C₆ H_(12-w) ((CR² R³)_(k) CR⁴ ═CR⁶ R⁷)_(w) +w (OC_(a) H_(2a) R_(f))₃ Si(CR⁸ R⁹)_(h) H!→C₆ H_(12-w) ((CR² R³)_(k) CR⁴ HCR⁶ R⁷ (CR⁸ r⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃)_(w)

For convenience the reaction of Equations denoted A or B above is chosen depending upon the commercial availability of the starting reagents. In each set of equations where an A and B are presented, h=0 in Eqn. A and k=0 in Eqn. B. Specific sources of reactants are listed hereinafter just prior to the Examples. A transition metal catalyst such as platinum, or a free radical initiatior is employed in an effective amount. Examples of suitable free radical initators include "VAZO" azo compounds available from E. I. du Pont de Nemours and Company, Wilmngton, Del.

These reactions can be conducted at a temperature of from about 25° C. to about 100° C. Preferably the process is conducted at about 80° C. to about 100° C. The pressure employed is typically ambient, about 1 atm (1.01×10⁵ Pa). The reactions are carried out under an inert gas atmosphere, although use of an air atmosphere is not precluded. Reaction time is typically from about 4 hours to about 24 hours.

Use of solvent is not required in these reactions. Suitable solvents which may be employed are those capable of dissolving the reactants, such as toluene or THF, and which do not interfere with the reaction or generate undesirable by-products. The desired product can be isolated by any means known to those skilled in the art. Preferably the desired product is isolated by removal of volatiles under reduced pressure.

NMR and mass spectrometry have been used to characterize product purities. Typically, yields of completed reacted material exceed 95%, with the prinicpal impurities being either reverse (Markovnikov) hydrosilyation or incompletely substituted material containing unreacted --CH═CH₂ groups.

The following show the preparation of compounds of formula I (k) (and IA(k) when replacing the group Si(OC_(a) H_(2a) R_(f))₃ with Si(R¹⁰)(OC_(a) H_(2a) R_(f))₂):

Eqn. 11A:

CR⁷ R⁶ ═CR⁴ (CR³ R²)_(k) (CF₂)_(v) (CR² R³)_(k) CR⁴ ═CR⁶ R⁷ +HSi(OC_(a) H_(2a) R_(f))₃ →(OC_(a) H_(2a) R_(f))₃ SiCR⁷ R⁶ CR⁴ H(CR³ R²)_(k) (CF₂)_(v) (CR² R³)_(k) CR⁴ HCR⁶ R⁷ --Si(OC_(a) H_(2a) R_(f))₃

Synthesis of the compounds of formula I(k) (and IA(k) when replacing the group Si(OC_(a) H_(2a) R_(f))₃ with Si(R¹⁰)(OC_(a) H_(2a) R_(f))₂) can also be realized by insertion of unsaturated trifluoroalkoxysilanes or trihalosilanes into the C--I bond of I(CF₂)_(v) I, followed by reduction of the C--I to C--H using standard organic reduction reagents, as shown below in Equation 11B. (P. Girard et al. in J. Am. Chem. Soc. (1980), vol 102, pp 2693-2698 describe the use of SmI₂ in reduction reactions.) Examples of suitable reagents are zinc metal, tri-n-butyl tin hydride or samarium iodide.

Eqn. 11B:

I(CF₂)_(v) I+2CR⁴ R⁵ ═CR⁶ (CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃ →(OC_(a) H_(2a) R_(f))₃ Si(CR⁹ R⁸)_(h) CR⁶ ICR⁵ R⁴ (CF₂)_(v) CR⁴ R⁵ CR⁶ I(CR⁸ R⁹)_(h) Si(OC_(a) H_(2a) R_(f))₃

which can be converted to the following with, for example, samarium iodide (Sml₂),

(OC_(a) H_(2a) R_(f))₃ Si(CR⁹ R⁸)_(h) CR⁶ HCR⁵ R⁴ (CF₂)_(v) CR⁴ R⁵ CR⁶ H(CR⁸ R⁹)_(h) (OC_(a) H_(2a) R_(f))₃.

Yields of the fluoroalkoxysilanes of formula I can be >99% using HSi(OCH₂ CF₃)₃ and CH₂ ═CHSi(OCH₂ CF₃)₃ ; slightly lower yields are found using HSi(OCH₂ C₃ F₇)₃ and CH₂ ═CHSi(OCH₂ F₇)₃. This is believed to be due to the steric demands of the large tris(heptafluorobutoxy)silanes. Some branching is observed due to Markovnikov (α) addition of the silyl hydride.

Hydrosilylation of HSi(OR¹⁰)₃, wherein R¹⁰ is defined above, onto polycarbosilane precursors, for example (Si(CH₂ CH₂ CH₂ Si(CH₂ CH═CH₂)₃)₄, leads to the formation of the "dendrimer" compounds of formula II. The synthesis of the dendrimers of formula II can start with the exhaustive allylation of tetrachlorosilane with a 10% excess of allylmagnesium bromide in diethyl ether (reflux, 4 h) to produce tetrallylsilane. The allyl groups of tetraallylsilane are hydrosilylated at room temperature for about 1-2 days with either trichlorosilane, dichloromethylsilane or chlorodimethylsilane (25% excess in the presence of a platinum catalyst, 10⁻⁴ to 10⁻⁵ mol per double bond) and an optional solvent, such as toluene or THF, to give the first generation dendrimers of formula II containing Si--Cl functional groups. Next, all the Si--Cl groups are replaced by SiCH₂ CH═CH₂ groups by reaction with an excess of allylmagnesium bromide in diethyl ether to produce dendrimers with 4 to 12 allyl end-groups. Hydrosilylation of these dendrimers by HSi(OCH₂ CF₃)₃, HSi(OCH₂ (CF₂)₂ CF₃)₃ or HSi(OCH₂ CH₃)₃ yields the dendrimers of formula II.

This route offers a unique flexibility; not only can the degree of branching be adjusted by replacing HSiCl₃ with HSiCl₂ CH₃ or HSiCl(CH₃)₂ in the initial hydrosilylation, but also the length of the branches can be varied. With similar high yields, for example, vinyl-based silane dendrimers can be prepared up to the fourth generation by using vinylmagnesium chloride in tetrahydrofuran (THF) in the alkenylation step. (See U.S. Pat. No. 5,276,110 incorporated by reference herein.) As an additional benefit the reactive Si-Cl end groups allow an easy functionalization of the dendrimer surface to produce formula II compounds by direct reaction with alcohols or fluoroalcohols.

The compounds of formula ImI are prepared by dissolving a fluorine-bearing silane, such as one having the formula Si(OCH₂ R_(f))₄, wherein R_(f) is as defined in formula III, or mixed silanes, such as Si(OCH₂ R_(f))_(x) (OR)_(4-x), wherein R is C₁ to about C₈ alkyl, and x=1-3, in a solvent in which water is soluble, such as isopropyl alcohol (IPA). A soluble source of fluoride ion, such as CsF, is added to the solution along with less than a 1.5:1 molar excess of water. The solution is maintained, with optional heating, until the water has been substantially consumed. The byproduct alcohols and any unreacted water are then removed from the system by, for instance, distillation. The remaining material is an oligomeric silicate with sufficient residual fluorine-bearing groups to be soluble in fluorinated solvents.

Alternatively, polysilicates of formula Imi can be made by combining a fluorine-bearing silane such as Si(OCH₂ C₃ F₇)₄ (FBS) with a stoichiometric deficiency (i.e., <2:1) of trifluoroacetic acid (TFA) or other strong fluorocarboxylic acid. The solution will generally be heated so as to promote extensive reaction between the silane and acid. Reaction byproducts (ester, alcohol and any unreacted acid) are then removed, for example, by distillation.

Preparation of the oligomeric compounds of formula IV can proceed in similar fashion. In the alternative process using a strong fluorocarboxylic acid, heating is optional.

Formula III and formula IV are an idealized formulas which correspond to 100% crosslinking of the SiOH group; however, there can be residual uncrosslinked SiOH groups during preparation. z is the molar ratio of water or other gelling agent to silane. R_(f) is preferably CF₃, C₂ F₅ or C₃ F₇ for formula III and C₆ F₁₃, n-C₈ F₁₇ and n-C₁₀ F₂₁ for formula IV and a is preferably 1 or 2.

Using trifluoroacetic acid and fluorinated solvents, the fluorine-bearing compounds of formula I, IA, II, ImI and IV of the present invention can be condensed into silica networks using non-aqueous sol-gel techniques. For example, the condensation of Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ C₃ F₇)₃ by CF₃ COOH in perfluoro(butyl THF) (FC-75) produces a clear gel, demonstrating that inorganic hybrid networks can be easily formed in fluorinated solvents. The advantage of using these new fluoroalkoxysilanes is that they are soluble in fluorinated solvents, thus one can manage sol-gel condensation and form inorganic/organic network materials using dissolved fluoropolymers in perfluorinated solvents such as hexafluorbenzene and perfluoro(butyl-THF) using trifluoroacetic acid in lieu of more conventional gelling agents. These network materials can then be used to coat a substrate, such as glass, to form a film. The fluorine-bearing compounds of formula I, IA, III and IV (and those of formula II that are soluble in fluorinated solvents) of the present invention can be also used in conjunction with dissolved fluoropolymers to provide semi-interpenetrating networks useful for a variety of applications including as primers for adhesion.

The compounds of formula II are useful in abrasion resistant materials, impact resistant glasses, and can act as crosslinking agents for some functionalized organic polymers.

EXAMPLES

All reactions were carried out in a Vacuum Atmospheres Co. dry box or under nitrogen. In the examples, all commercial reagents were distilled prior to use. Trichlorosilane, tetravinylsilane, tetrachlorosilane, vinyltrichlorosilane, allyltrichlorosilane, 1,3,5,7-tetramethylcyclotetra-siloxane, tetrakis(dimethylsiloxy)-silane, 1,1,3,3-tetramethyldisiloxane, and 1,3,5,7,9-pentamethylcyclo-pentasiloxane were purchased from Aldrich Chemical Co., Milwaukee, Wis., Huls America Inc., Piscataway, N.J. or PCR Inc. Gainesville, Fla. Trifluoroethanol and n-heptafluorobutanol were obtained from PCR Inc. Si(OCH₂ CF₃)₄, Si(OCH₂ (CF₂)CF₃)₄, HSi(OCH₂ CF₃)₃, CH₂ ═CHSi(OCH₂ CF₃)₃, Si(CH₂ CH₂ CH₂ Si(CH₃)₂ CH₂ CH═CH₂)₄, Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH═CH₂)₂)₄, and Si(CH₂ CH₂ CH₂ Si(CH₂ CH═CH₂)₃)₄ were synthesized by slight modifications of published procedures. Platinum divinylsiloxane complex (3-3.5% Pt concentration in xylene, Huls PC₀₇₂) was obtained from Huls America Inc. and diluted 5:1 by volume (toluene, Pt complex) prior to use. Toluene and tetrahydrofuran was reagent grade and purified by distillation from calcium hydride prior to use. Tetraallylsilane was synthesized by a modification of a published procedure (J. Organomet. Chem., 84 (1975), pp 199-229). Vinylpolyfluoroalkanes were prepared from I(CF₂)₆ I available from PCR Inc. "FLUORINERT" FC-75 and "FLUORINERT" FC-40 solvents were obtained from PCR Inc. Hexafluorobenzene was obtained from Aldrich Chemical, Inc. The mass spectroscopy experiments were performed on a Finnigan 4615B GC/MS quadrupole mass spectrometer (San Jose, Calif.). An electron impact source configuration operating at 200° C. and a source pressure of 1.0×10⁻⁶ Torr was used. The mass spectrometer was scanned at a rate of about 1000 Daltons/second. All mass spectral peaks were recorded as sum of the ion plus potassium (M+39). Proton and carbon NMR were determiined on a GE model QE-300 instrument. Elemental analyses were performed by Oneida Research Services Inc., One Halsey Road, Whitesboro, N.Y.

The following are abbreviations used in the description and the examples:

Et--ethyl

FBS=tetra(heptafluorobutoxy)silane, Si(OCH₂ C₃ F₇)₄

FC-75=perfluoro(butyl THF)

FES=tetra(trifluoroethoxy)silane, Si(OCH₂ CF₃)₄

HFB=hexafluorobenzene, C₆ F₆

HFBS=tri(heptafluorobutoxy)silane, HSi(OCH₂ C₃ F₇)₃

Me=methyl, CH₃

PP-11=perfluoro phenanthrene

TEOS=tetraethoxysilane, Si(OCH₂ CH₃)₄

TFA=trifluoroacetic acid, CF₃ COOH

THF=tetrahydrofuran

Example 1 Synthesis of Si(CH₂ CH₂ Si(OCH₂ CF₃)₃)₄

A mixture of 2.39 g (7.34 mmol) of HSi(OCH₂ CF₃)₃, 2 drops of Pt catalyst and 0.255 g (1.87 mmol) of tetravinylsilane was heated to 90° C. for 6 hr. After cooling, the residual silane was removed in vacuo leaving a brownish oil which was identified as Si(CH₂ CH₂ Si(OCH₂ CF₃)₃)₄. MS (m/3) 1480 (M +39, 100%), 1153 ((H₂ C═CH)Si(CH₂ CH₂ Si(OCH₂ CF₃)₃)₃ +39, 20%). ¹³ C NMR(C₆ D₆) 1.31, 1.86, 2.31, 2.53 (SiCH₂), 61.8 (q, CH₂ CF₃, ² J(CF)=36.6 Hz), 124.53 (q, CF₃, ¹ J(CF)=277.9 Hz). Small amounts of --SiCH(CH₃)Si(OCH₂ CF₃)₃ groups due to Markovnikov addition (-0.55, 7.79 ppm) were observed.

Example 2 Synthesis of Si(CH₂ CH₂ Si(OCH₂ (CF₉)₂ CF₃)₃)₄

The reaction was performed in a manner similar to Example 1 using 0.250 g (1.83 mmol) of tetravinylsilane and 4.597 g (7.34 mmol) of HSi(OCH₂ (CF₂)₂ CF₃)₃. Workup yielded Si(CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃)₄ as a brownish oil. ¹³ C NMR(THF-d₈)1.47, 2.06, 2.32, 2.64 (SiCH₂), 61.5 (t, CH₂ CF₂, ² J(CF)=27.2 Hz), 110-120 (M, (CF₂)₂ CF₃). Small amounts of--SiCH(CH₃)Si(OCH₂ (CF₂)₂ CF₃)₃ groups due to Markovnikov addition (-0.4, 7.87 ppm) were observed.

Example 3 Synthesis of Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄

A solution consisting of 0.497 g (1.51 mmol) of Si(OSi(CH₃)₂ H)₄, 2.149 g (6.10 mmol) of CH₂ ═CHSi(OCH₂ CF₃)₃ and two drops of Pt catalyst was heated to 90° C. for 6 hr. After cooling, the solution was stirred an additional 16 hr at room temperature. Removal of all volatiles in vacuo gave the product, Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄, in quantitative yield. Small amounts of --SiCH(CH₃)Si(OCH₂ CF₃)₃ groups due to Markovnikov addition were also observed by NMR. ¹³ C NMR(C₆ D₆) -0.636, -0.603 (major isomer, CH₃ Si), 1.47 (minor isomer, CH₃ Si), 2.10 (SiCH₂), 7.37 (SiCH), 7.40 (CH₃ CH), 9.03 (SiCH₂), 62.14 (q (major), CH₂ CF₃, ² J(CF)=36.5 Hz), 62.21 (q (minor), CH₂ CF₃, ² J(CF)=36.5 Hz), 125.16 (q, CF₃, ¹ J(CF)=277.7 Hz). MS (m/e) 1736 (M+39, 100%)

Example 4 Synthesis of Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃)₄

The reaction was performed in a manner similar to Example 3 using 10.049 g (15.4 mmol) of CH₂ ═CHSi(OCH₂ (CF₂)₂ CF₃)₃, 1.241 g (3.78 mmol) of Si(OSi(CH₃)₂ H)₄, and three drops of Pt catalyst in 10 ml of toluene. Workup yielded 9.95 g (90%) of Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃)₄ as the sole product. ¹³ C NMR(THF-d₈)-0.797, -0.753 (major isomer, CH₃ Si), 1.03, 1.40, 1.48 (minor isomer, CH₃ Si), 2.04 (SiCH₂), 6.62 (SiCH), 7.30 (CH₃ CH), 8.89, 8.93 (SiCH₂), 61.61 (t, CH₂ CF₃, ² J(CF)=27.6 Hz), 105-120 (m, CF₃ (CF₂)₂). MS (m/e) 2975 (M+39).

Example 5 Synthesis of Si(OSi(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄

A mixture consisting of 3.003 g (8.20 mmol) of CH₂ ═CHCH₂ Si(OCH₂ CF₃)₃, 0.672 g (2.04 mmol) of Si(OSi(CH₃)₂ H)₄ and one drop of Pt catalyst was heated to 90° C. for 4 hrs, then cooled and stirred at room temperature for 16 hr. The volatiles were removed in vacuo leaving 3.44 g (94%) of a yellow tinted liquid identified as Si(OSi(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄. ¹ H NMR (C₆ D₆) 0.26 (s, 6H), 0.72 (m, 4H), 1.61 (m, 2H), 3.71 (q, 6H). ¹³ C NMR (C₆ D₆) -0.53, -0.12 (s, SiCH₃), 14.07, 16.78, 16.81 (SiCH₂), 61.53 (q, CH₂ CF₃, ² J(CF)=36.5 Hz). A small amount of Markovnikov addition product was also observed by NMR.

Example 6 Synthesis of cyclo-((CH)(CF₃ CH₂ O)₃ SiCH₂ CH₂ CH₂)SiO₄)

A mixture consisting of 3.595 g (9.82 mmol) of cyclo-CH₂ ═CHCH₂ Si(OCH₂ CF₃)₃, 0.525 g (2.18 mmol) of ((CH₃)(H)SiO)₄ and one drop of Pt catalyst was heated to 90° C. for 4 hrs, then cooled and stirred at room temperature for 16 hr. The volatiles were removed in vacuo leaving 3.94 g of a brown-tinted liquid identified as cyclo-((CH₃)(CF₃ CH₂ O)₃ SiCH₂ CH₂ CH₂)SiO)₄. ¹ H NMR (C₆ D₆) 0.30 (m, 6H), 0.75 (m, 4H), 1.62 (m, 2H), 3.60 (q, 6H). ¹³ C NMR (C₆ D₆) -1.12 (s, SiCH₃), 13.67, 16.58, 21.41 (SiCH₂), 61.52 (q, CH₂ CF₃, ² J(CF)=36.3 Hz). Some minor peaks were observed in the ¹³ C NMR due to Markovnikov addition products.

Example 7 Synthesis of cyclo-((CH₃)(CF₃ CH₂ O)₃ SiCH₂ CH₂ CH₂)SiO₅)

A mixture consisting of 3.003 g (8.20 mmol) of CH₂ ═CHCH₂ Si(OCH₂ CF₃)₃, 0.493 g (1.64 mmol) of cyclo-((CH₃)(H)SiO)₅ and one drop of Pt catalyst was heated to 90° C. for 4 hrs, then cooled and stirred at room temperature for 16 hr. The volatiles were removed in vacuo leaving 3.11 g (89%) of a thick yellow-tinted liquid identified as cyclo-((CH₃)(CF₃ CH₂ O)₃ SiCH₂ CH₂ CH₂)SiO)₅. ¹ H NMR (THF-d₈) 0.18 (s, 3H), 0.68 (m, 2H), 0.90 (m, 2H), 1.59 (m, 2H), 4.22 (q, 6H). A small amount of Markovnikov addition product was also observed by NMR.

Example 8 Synthesis of cyclo-((CH₃)((CF₃ CH₂ O)₃ SiCH₂ CH₂)SiO)₄

The reaction was performed in a similar manner to Example 3 using 0.525 g (1.53 mmol) of cyclo-((CH₃)(CH₂ ═CH)SiO)₄, 2.00 g (6.22 mmol) of HSi(OCH₂ CF₃)₃ and two drops of Pt catalyst. Workup yielded ((CH₃)((CF₃ CH₂ O)₃ SiCH₂ CH₂)SiO)₄ as an oil. Some trisubstituted product was observed in the mass spectrum. ¹³ C NMR(C₆ D₆) -1.38, 1.29 (s, CH₃ Si), 1.90 (SiCH₂), 7.95 (SiCH₂), 62.14 (q (major), CH₂ CF₃, ² J(CF)=36.5 Hz), 61.83 (q (minor), CH₂ CF₃, 2J(CF)=36.6 Hz), 124.53 (q, CF₃, ¹ J(CF)=278.0 Hz). MS (m/e) 1687 (M+39, 100%), 1361 (trisubstituted product +39, 12%).

Example 9 Synthesis of cyclo-((CH₃)(CF₃ (CF₂)₂ CH₂ O)₃ SiCH₂ CH₂)SiO₄)

This reaction was performed in a manner similar to that in Example 3 using 0.500 g (1.45 mmol) of cyclo-((CH₃)(CH₂ ═CH)SiO)₄, 3.64 g (5.81 mmol) of HSi(OCH₂ (CF₂)₂ CF₃)₃ and two drops of Pt catalyst. Workup yielded ((CH₃)((CF₃ (CF₂)₂ CH₂ O)₃ SiCH₂ CH₂)SiO)₄ as an oil. Some trisubstituted product (4-5%) was observed by NMR. ¹³ C NMR(THF-d₈) -1.70, -1.65 (s, CH₃ Si), 1.75 (SiCH₂), 7.80, 7.88 (SiCH₂), 61.55 (t, CH₂ CF₃, ² J(CF)=27.6 Hz), 105-120 (m, CF₃ (CF₂)₂).

Example 10 Synthesis of (CF₃ CH₂ O)₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si(OCH₂ CF₃)₃

This preparation was done in a manner similar to Example 3 using 0.258 g (0.782 mmol) of (CH₂ ═CH(CF₂)₃)₂, 0.526 g (1.61 mmol) of HSi(OCH₂ CF₃)₃ and two drops of Pt catalyst. Workup yielded ((CF₃ CH₂ O)₃ SiCH₂ CH₂ (CF₂)₃)₂ as the sole product by NMR. ¹ H NMR(C₆ D₆) 0.68-0.79, 2.0-2.1 (m, AA'BB' pattern, SiCH₂ CH₂ Si), 3.51 (q, CH₂ CF₃). ¹³ C NMR(C₆ D₆) 0.685 (s, CH₂ Si), 25.03 (t, CH₂ CF₂), 61.74 (q, CH₂ CF₃, 2J(CF)=34.8 Hz), 105-120 (m, (CF₂)₆), 124.28 (q, CF₃, ¹ J(CF)=277.9 Hz). MS (m/e) 1045 (M+39, 100%).

Example 11 Synthesis of (CF₃ (CF₂)₂ CH₂ O)₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃

This preparation was done in a manner similar to Example 3 using 0.252 g (0.713 mmol) of CH₂ ═CH(CF₂)₆ CH═CH₂, 0.998 g (1.59 mmol) of HSi(OCH₂ (CF₂)₂ CF₃)₃ and three drops of Pt catalyst. The mixture was heated to 120° C. for 12 hr. Workup yielded (CF₃ (CF₂)₂ CH₂ O)₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃ as the sole product by NMR. ¹ H NMR (THF-d₈) 1.1-1.3, 2.18-2.4 (m, AA'BB' pattern, SiCH₂ CH₂ Si), 4.48 (t, CH₂ CF₂). ¹³ C NMR(THF-d₈) 0.678 (s, CH₂ Si), 61.64 (t, OCH₂ CF₂, ² J(CF)=27.8 Hz), 105-120 (m, CF₂, CF₃), resonance for CH₂ CF₂ is about 25 ppm and is obscured by solvent. MS (m/e) 1645 (M+39, 100%), 1019 (monosubstituted product +39,2%).

Example 12 Synthesis of (CF₃ CH₂ O)₃ Si(CH₂)₆ (CF₂)₆ (CH₂)₆ Si(OCH₂ CF₃)₃

A mixture consisting of 2.002 g (4.29 mmol) of (CH₂ ═CH(CH₂)₄ (CF₂)₃)₂, 2.82 g (8.64 mmol) of HSi(OCH₂ CF₃)₃ and 10 microliters of Pt catalyst was heated to 90° C. for 4 hr, cooled and stirred for 16 h. The excess silane was removed in vacuo yielding 3.98 g (83%) of a thick liquid identified as (CF₃ CH₂ O)₃ Si(CH₂)₆ (CF₂)₆ (CH₂)₆ Si(OCH₂ CF₃)₃. ¹ H NMR (C₆ D₆) 0.42 (m, SiCH₂), 0.82-1.09 (m, CH₂ CH₂), 1.20 (m, CH₂), 1.38 (m, CH₂), 1.62-1.90 (m, CH₂ CF₂), 3.59 (q, CH₂ CF₃). ¹³ C NMR (C₆ D₆) 9.66 (CH₂ Si), 20.59, 22.19 28.89 (CH₂), 31.0 (t, CH₂ CF₂), 32.6 (CH₂), 61.54 (q, CH₂ CF₃, ² J(CF)=36.5 (q, CF₃).

Example 13 Synthesis of (CF₃ (CF₂)₂ CH₂ O)₃ Si(CH₂)₆ (CF₂)₆ (CH₂)₆ Si(OCH₂ (CF₂)₂ CF₃)₃

A mixture consisting of 1.254 g (2.69 mmol) of (CH₂ ═CH(CH₂)₄ (CF₂)₃)₂, 3.37 g (5.38 mmol) of HSi(OCH₂ (CF₂)₂ CF₃)₃ and 10 microliters of Pt catalyst was heated to 90° C. for 4 hr, cooled and stirred for 16 h. The excess silane was removed in vacuo yielding 3.69 g (97%) of a thick, colorless liquid identified as (CF₃ (CF₂)₂ CH₂ O)₃ Si(CH₂)₆ (CF₂)₆ (CH₂)₆ Si(OCH₂ (CF₂)₂ CF₃. ¹ H NMR (THF-d₈) 0.90 (m, SiCH₂), 1.40 (m, CH₂), 1.40-1.68 (m, (CH₂)₃), 2.03-2.23 (m, CH₂ CF₂), 4.40 (t, CH₂ CF₂). ¹³ C NMR(C₆ D6) 9.73 (CH₂ Si), 21.04, 22.63, 29.49 (CH₂), 31.66 (t, CH₂ CF₂), 33.22 (CH₂), 61.35 (t, CH₂ CF₃, ² J(CF)=24.7 Hz), 107-120 (q, CF₂ resonances).

Example 14 Synthesis of Si(CH₂ CH₂ CH₂ Si(CH₃)CH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃)₄

Triethoxysilane (5.567 g, 0.034 mol) was added to 5.023 g (8.47 mmol) of Si(CH₂ CH₂ CH₂ Si(CH₃)₂ CH₂ CH═CH₂)₄ and 50 microliters of Pt catalyst and heated to reflux for 5 hr. After cooling, an additional 2.796 g (0.0017 mol) of triethoxysilane and one drop of Pt catalyst solution was added, and the solution was refluxed an additional 8 hr and cooled. The excess triethoxysilane was removed in vacuo leaving 7.78 g (74%) of a tea colored liquid identified as Si(CH₂ CH₂ CH₂ Si(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃)₄. Approximately 20% of product due to Markovnikov addition were observed. ¹ H NMR(C₆ D₆) -0.01 (s, SiCH₃), 0.19 (s, SiCH₃ Markovnikov product), 0.58-0.86 (m, CH₂), 1.15 (t, OCH₂), 1.4-1.8 (m, CH₂), 3.76 (q, CH₃). ¹³ C NMR(C₆ D₆) -2.59 (SiCH₃), -2.17 (SiCH₃, Markovnikov product), 16.14, 18.52, 19.62, 20.40, 21.21 (CH₂), 19.08 (CH₃), 58.7 (OCH₂).

Example 15

Synthesis of Si(CH, CH₂ CH₂ Si(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄

To a mixture containing 1.998 g (3.37 mmol) of Si(CH₂ CH₂ CH₂ Si(CH₃)₂ CH₂ CH═CH₂)₄ and 30 microliters of Pt catalyst solution was added 6.602 g (0.020 mol) of HSi(OCH₂ CF₃)₃ dropwise over a period of 0.5 hr. After the addition, the mixture was heated to 90° C. for 6 hr and stirred at room temperature for 16 hr. After removing the excess silane in vacuo, and filtering through activated charcoal, 57.4 g (90%) of Si(CH₂ CH₂ CH₂ Si(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ was obtained as a thick tea-colored liquid. ¹ H NMR(C₆ D₆) 0.08 (s, SiCH₃), 0.51-0.84 (m, CH₂), 1.40-1.62 (m, CH₂), 3.70 (q, CH₂ CF₃). ¹³ C NMR(C₆ D₆) -3.04 (SiCH₃), 14.24, 17.11, 18.50, 19.55, 19.93, 20.98 (CH₂), 61.52 (CH₂ CF₃, ² J(CF)=36.6 Hz), 124.5 (CF₃, ¹ J(CF)=278 Hz).

Example 16 Synthesis of Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃)₂)₄

A mixture containing 5.011 g (7.18 mmol) of Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH═CH₂)₂)₄, 7.035 g (0.043 mol) of triethoxysilane and 30 microliters of Pt catalyst solution was heated to reflux for 5 hr. After checking by NMR, an additional 2.364 g (0.014 mol) of triethoxysilane and 1 drop of Pt catalyst solution were added, and the resulting mixture was refluxed for 8 hr. After cooling and removing the excess silane in vacuo, 10.74 g (74%) of Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃)₂)₄ was obtained as a tea-colored liquid. Aproximately 20% of product due to Markovnikov addition were observed. ¹ H NMR (C₆ D₆) -0.02 (s, SiCH₃), 0.08 (s, SiCH₃) Markovnikov product) 0.58-0.82 (m, CH₂), 1.13 (t, CH₃), 1.38-1.80 (m, CH₂), 3.77 (q, CH₂ CH₃). ¹³ C NMR(C₆ D₆) -4.40 (SiCH₃), -4.14 (SiCH₃ Markovnikov), 16.25, 18.57, 18.70, 18.78, 19.62, 20.33 (CH₂), 19.07 (CH₃), 59.78 (OCH₂).

Example 17 Synthesis of Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₂)₄

To a mixture containing 1.515 g (2.17 mmol) of Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH═CH₂)₂)₄ and six drops of Pt catalyst solution dissolved in 20 ml of toluene was added 7.098 g (0.022 mol) of HSi(OCH₂ CF₃)₃ dropwise over a period of 0.5 hr. After the addition, the mixture was heated to 100° C. for 8 hr. After cooling, NMR showed the reaction to be incomplete and an additional 0.718 g (2.2 mmol) of HSi(OCH₂ CF₃)₃ and 1 drop of Pt catalyst were added. This mixture was heated to 110° C. for 6 hr and stirred at room temperature for 64 hr. After removing the excess silane in vacuo, 5.23 g (73%) of Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₂)₄ was obtained as a thick orange-tinted liquid. ¹³ C NMR(C₆ D₆) -5.07 (SiCH₃), 14.35, 17.48, 18.42, 19.50, 19.62, 23.08 (CH₂), 61.90 (CH₂ CF₃, ² J(CF)=36.7 Hz), 124.6 (CF₃, ¹ J(CF)=278 Hz).

Example 18 Synthesis of Si(CH₂ CH₂ CH₂ Si(CH₂ CH₂ CH₂ Si(OCH₂ CF)₃)₃)₄

A mixture containing 1.853 g (2.31 mmol) of Si(CH₂ CH₂ CH₂ Si(CH₂ CH═CH₂)₃)₄, 12.091 g (37.07 mmol) of HSi(OCH₂ CF₃)₃, and 10 drops of Pt catalyst solution in 10 ml of toluene was heated to reflux for 6 hr followed by stirring at room temperature for 90 hr. The mixture was heated an additional 4 hr and cooled. After removing the excess silane in vacuo, 7.92 g (73%) of Si(CH₂ CH₂ CH₂ Si(CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₃)₄ was obtain as a thick orange-tinted liquid. ¹ H NMR (toluene-d₈) 0.59-1.00 (m, CH₂), 1.40-1.75 (m, CH₂), 3.82 (broad q, CH₂ CF₃). ¹³ C NMR(C₆ D₆) 14.08, 16.53, 17.18, 18.0, 18.5, (CH₂, remaining line obscured by toluene), 61.30 (CH₂ CF₃, ² J(CF)=36.6 Hz), 124.2 (CF₃, ¹ J(CF)=278 Hz).

Example 19 Preparation of Polysilicates from FBS

FBS/2-propanol/deionized water/0.5% CsF in 2-propanol were combined with mixing in the sequence given at the following levels by weight, 82.2%/14.2%/2.4%/1.2%. The final solution contained a water/FBS molar ratio of 1.33 and 6.07 wt. % solids. This solution was heated slowly for two hours until volatile products could be removed by distillation. After 30 min. of distillation, the flask was allowed to cool and the contents analyzed by gas chromatography. The analysis indicated that water had essentially completely reacted. The cooled material was allowed to evaporate at room temperature until it had lost 35% of its original weight.

The concentrated material was used to make up solutions in hexafluorobenzene (8.6%) and in FC-75 (8.9%). Both were very homogeneous and formed clear films when flow or dip coated on glass slides.

Silicon-29 NMR was run on the concentrate and indicated substantial reaction of the starting material (ca. 90%) to form a broad range of polysilicates with Q1 through Q4 structures (Si atom has 1 to 4 bonds to other Si atoms through oxygen). (Many of the species must contain residual fluorine-bearing groups in order for the solubility in fluorinated solvents to be observed.) 

What is claimed is:
 1. A compound having the formula

    X(Si(Oc.sub.a H.sub.2a R.sub.f).sub.3).sub.n               I

wherein: X is at least one organic link selected from the group consisting of:(a) R¹ _(m) SiY_(4-m) ; (b) ring structures ##STR3## (c) R¹ _(m) Si(OSi(CH₃)₂ Y)_(4-m) ; (d) CH₃ SiY₂ OSiY₂ CH₃ ; (e) Y₃ SiOSiY₃ ; (f) Y₂ (CH₃)Si(CH₂)_(b) Si(CH₃)Y₂ ; (g) Y₃ Si(CH₂)_(b) SiY₃ ; (h) Y₃ SiC₆ H₄ SiY₃ ; (i) substituted benzene, including all isomers, selected from the group consisting of:(i) C₆ H₃ (SiZ_(3-c) Y_(c))₃ ; (ii) C₆ H₂ (SiZ_(3-c) Y_(c))₄ ; (iii) C₆ H(SiZ_(3-c) Y_(c))₅ ; and (iv) C₆ (SiZ_(3-c) Y_(c))₆ ; and (j) substituted cyclohexane, including all stereoisomers, selected from the group consisting of:(i) 1,2-C₆ H₁₀ (Y)₂ ; 1,3-C₆ H₁₀ (Y)₂ ; 1,4-C₆ H₁₀ (Y)₂ ; (ii) 1,2,4-C₆ H₉ (Y)₃ ; 1,2,3-C₆ H₉ (Y)₃ ; 1,3,5-C₆ H₉ (Y)₃ ; (iii) 1,2,3,4-C₆ H₈ (Y)₄ ; 1,2,4,5-C₆ H₈ (Y)₄ ; 1,2,3,5-C₆ H₉ (Y)₄ ; (iv) 1,2,3,4,5-C₆ H₇ (Y)₅ ; and (v) C₆ H₆ (Y)₆ ; (k) Y(CF₂)_(v) Y R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:(a) C₁ to about C₁₈ perfluoroalkyl; (b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1; (c) --CF₂ --(CF₂ --O)_(q) --CF₃, wherein q is an integer of at least 2; and (d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ; wherein up to 50% of the fluorine of the R_(f) group is optionally substituted with hydrogen; a is an integer from 1 to about 10; b is an integer from 1 to about 10; c is 1, 2 or 3; m is 0, 1 or 2; n is an integer greater than or equal to 2; v is an even integer from 2 to about 14; R¹ is C₁ to about C₈ alkyl or aryl; Y is --(CR² R³)_(k) CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_(h) -- R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl, or aryl, provided that at least one of R⁴ to R⁷ is hydrogen; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; Z is C₁ to about C₄ alkyl, 3,3,3-trifluoropropyl, aralkyl or aryl.
 2. The compound of claim 1 wherein X is selected from the group consisting of: R¹ _(m) SiY_(4-m) ; ##STR4## R¹ _(m) Si(OSi(CH₃)₂ Y)_(4-m) and Y(CF₂)_(v) Y; and R_(f) is CF₃, C₂ F₅ or C₃ F₇.
 3. The compound of claim 2 selected from the group consisting of:Si(CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ ; Si(CH₂ CH₂ Si(OCH₂ CF₂ CF₃)₃)₄ ; Si(CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃)₄ ; Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ ; Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃)₄ ; Si(OSi(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ ; cyclo-((CH₃)(CF₃ CH₂ O)₃ SiCH₂ CH₂)SiO)₄ ; cyclo-((CH₃)(CF₃ CH₂ O)₃ SiCH₂ CH₂ CH₂)SiO)₄ ; cyclo-((CH₃)(CF₃ CH₂ O)₃ SiCH₂ CH₂ CH₂)SiO)₅ ; cyclo-((CH₃)(CF₃ (CF₂)₂ CH₂ O)₃ SiCH₂ CH₂)SiO)₄ ; (CF₃ CH₂ O)₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si(OCH₂ CF₃)₃ ; (CF₃ (CF₂)₂ CH₂ O )₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si(OCH₂ (CF₂)₂ CF₃)₃ ; and (CF₃ CH₂ O)₃ Si(CH₂)₆ (CF₂)₆ (CH₂)₆ Si(OCH₂ CF₃)₃.
 4. A compound having the formula

    X(R.sup.10 Si(OC.sub.a H.sub.2a R.sub.f).sub.2).sub.n      IA

wherein: X is at least one organic link selected from the group consisting of:(a) R¹ _(m) SiY_(4-m) ; (b) ring structures ##STR5## (c) R¹ _(m) Si(OSi(CH₃)₂ Y)_(4-m) ; (d) CH₃ SiY₂ OSiY₂ CH₃ ; (e) Y₃ SiOSiY₃ ; (f) Y₂ (CH₃)Si(CH₂)_(b) Si(CH₃)Y₂ ; (g) Y₃ Si(CH₂)_(b) SiY₃ ; (h) Y₃ SiC₆ H₄ SiY₃ ; (i) substituted benzene, including all isomers, selected from the group consisting of:(i) C₆ H₃ (SiZ_(3-c) Y_(c))₃ ; (ii) C₆ H₂ (SiZ_(3-c) Y_(c))₄ ; (iii) C₆ H(SiZ_(3-c) Y_(c))₅ ; and (iv) C₆ (SiZ_(3-c) Y_(c))₆ ; and (j) substituted cyclohexane, including all stereoisomers, selected from the group consisting of:(i) 1,2-C₆ H₁₀ (Y)₂ ; 1,3-C₆ H₁₀ (Y)₂ ; 1,4-C₆ H₁₀ (Y)₂ ; (ii) 1,2,4-C₆ H₉ (Y)₃ ; 1,2,3-C₆ H₉ (Y)₃ ; 1,3,5-C₆ H₉ (Y)₃ ; (iii) 1,2,3,4-C₆ H₈ (Y)₄ ; 1,2,4,5-C₆ H₈ (Y)₄ ; 1,2,3,5-C₆ H₉ (Y)₄ ; (iv) 1,2,3,4,5-C₆ H₇ (Y)₅ ; and (v) C₆ H₆ (Y)₆ ; R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:(a) C₁ to about C₁₈ perfluoroalkyl; (b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1; (c) --CF₂ (CF₂ O)_(q) --CF₃, wherein q is an integer of at least 2; and (d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ; each R_(f) optionally substituted with one or more hydrogen; Z is C₁ to about C₄ alkyl, 3,3,3-trifluoropropyl, aralkyl or aryl; Y is --(CR² R³)_(k) CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_(h) --; R¹ is C₁ to about C₈ alkyl or aryl; R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl or aryl, provided that at least one of R⁴ to R⁷ is hydrogen; R¹⁰ is C₁ to about C₈ alkyl or C_(a) H_(2a) R_(f) ; m is 0, 1 or 2; k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; a is an integer from 1 to about 10; b is an integer from 1 to about 10; c is 1,2 or 3; and n is an integer greater than or equal to
 2. 5. The compound of claim 4 wherein X is selected from the group consisting of: R¹ _(m) SiY_(4-m) ; ##STR6## R¹ _(m) Si(OSi(CH₃)₂ Y)_(4-m) and Y(CF₂)_(v) Y; and R_(f) is CF₃, C₂ F₅ or C₃ F₇.
 6. The compound of claim 5 selected from the group consisting of:Si(CH₂ CH₂ SiCH₃ (CH₂ CF₃)₂)₄ ; Si(CH₂ CH₂ SiCH₃ (OCH₂ (CF₂)₂ CF₃)₂)₄ ; Si(OSi(CH₃)₂ CH₂ CH₂ SiCH₃ (OCH₂ CF₃)₂)₄ ; Si(OSi(CH₃)₂ CH₂ CH₂ SiCH₃ (OCH₂ (CF₂)₂ CF₃)₂)₄ ; Si(OSi(CH₃)₂ CH₂ CH₂ CH₂ SiCH₃ (OCH₂ CF₃)₂)₄ ; (CF₃ CH₂ O)₂ CH₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ SiCH₃ (OCH₂ CF₃)₂ ; (CF₃ (CF₂)₂ CH₂ O)₂ CH₃ SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ SiCH₃ (OCH₂ (CF₂)₂ CF₃)₂ ; (CF₃ CH₂ O)₂ CH₃ Si(CH₂)₆ (CF₂)₆ (CH₂)₆ SiCH₃ (OCH₂ CF₃)₂ ; Si(CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ CF₃)₂)₄ ; Si(CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ (CF₂)₂ CF₃)₂)₄ ; Si(OSi(CH₃)₂ CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ CF₃)₂)₄ ; Si(OSi(CH₃)₂ CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ (CF₂)₂ CF₃)₂)₄ ; Si(OSi(CH₃)₂ CH₂ CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ CF₃)₂)₄ ; (CF₃ CH₂ O)₂ (CF₃ CF₂ CH₂ CH₂)SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ CF₃)₂ ; (CF₃ (CF₂)₂ CH₂ O)₂ (CF₃ CF₂ CH₂ CH₂)SiCH₂ CH₂ (CF₂)₆ CH₂ CH₂ Si (CH₂ CH₂ CF₂ CF₃)(OCH₂ (CF₂)₂ CF₃)₃ ; (CF₃ CH₂ O)₂ (CF₃ CF₂ CH₂ CH₂)Si(CH₂)₆ (CF₂)₆ (CH₂)₆ Si(CH₂ CH₂ CF₂ CF₃)(OCH₂ CF₃)₂ ; and cyclo-((CH₃)(CF₃ CH₂ O)₂ CH₃ SiCH₂ CH₂)SiO)₄ ; cyclo-((CH₃)(CF₃ CH₂ O)₂ CH₃ SiCH₂ CH₂ CH₂)SiO)₄ ; cyclo-((CH₃)(CF₃ CH₂ O)₂ CH₃ SiCH₂ CH₂ CH₂)SiO)₅ ; and cyclo-((CH₃)(CF₃ (CF₂)₂ CH₂ O)₂ SiCH₂ CH₂)SiO)₄.
 7. A compound having the formula

    Si (CH.sub.2).sub.f Si(CH.sub.3).sub.3-d ((CH.sub.2).sub.e Si(OR.sup.10)).sub.d !.sub.4                              II

wherein: dis 1, 2 or 3; e is an integer from 2 to about 10; f is an integer from 2 to about 10; R¹⁰ is C₁ to about C₈ alkyl or C_(a) H_(2a) R_(f) ; R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:(a) C₁ to about C₁₈ perfluoroalkyl; (b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1; (c) --CF₂ --(CF₂ --O)_(q) --CF₃, wherein q is an integer of at least 2; and (d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ; wherein up to 50% of the fluorine of the R_(f) group is optionally substituted with hydrogen; a is an integer from 1 to about
 10. 8. The compound of claim 7 wherein R¹⁰ is C_(a) H_(2a) R_(f).
 9. The compound of claim 8 selected from the group consisting of:Si(CH₂ CH₂ CH₂ Si(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃)₄ ; Si(CH₂ CH₂ CH₂ Si(CH₃)₂ CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ ; Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH₂ CH₂ Si(OCH₂ CH₃)₃)₂)₄ ; Si(CH₂ CH₂ CH₂ SiCH₃ (CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₂)₄ ; and Si(CH₂ CH₂ CH₂ Si(CH₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₃)₄.
 10. An oligomeric compound having the formula

    Si(OC.sub.a H.sub.2a R.sub.f).sub.4-z O.sub.z/2            I

wherein: z is a number from 0.5 to 3.0; a is an integer from 1 to about 10; and R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:(a) C₁ to about C₁₈ perfluoroalkyl; (b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1; (c) --CF₂ --(CF₂ O)_(q) --CF₃, wherein q is an integer of at least 2; and (d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ; wherein up to 50% of the fluorine of the R_(f) group is optionally substituted with hydrogen.
 11. The compound of claim 10 wherein R_(f) is CF₃, C₂ F₅, or C₃ F₇, and a is 1 or
 2. 12. An oligomeric compound having the formula

    R.sub.f --(CH.sub.2).sub.y --Si(OR.sup.14).sub.3-z O.sub.z/2IV

wherein: z is a number from 0.5 to 2.5; y is an integer from 2 to about 10; each R¹⁴ is independently C₁ to about C₈ alkyl, C₁ to about C₁₀ carboxy, C₁ to about C₁₀ fluorocarboxy or C_(a) H_(2a) R_(f) ; a is an integer from 1 to about 10; and R_(f) has up to about 18 carbon atoms and is selected from the group consisting of:(a) C₁ to about C₁₈ perfluoroalkyl; (b) -- CF₂ CF(CF₃)O!_(r) --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1; (c) --CF₂ --(CF₂ --O)_(q) --CF₃, wherein q is an integer of at least 2; and (d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ; wherein up to 50% of the fluorine of the R_(f) group is optionally substituted with hydrogen.
 13. The oligomeric compound of claim 12 wherein R_(f) is C₆ F₁₃, n-C₈ F₁₇ or n-C₁₀ F₂₁, and a is 1 or
 2. 